EP0543752A1 - Process for preparing metal carbides of high specific surface from activated carbon foams - Google Patents
Process for preparing metal carbides of high specific surface from activated carbon foams Download PDFInfo
- Publication number
- EP0543752A1 EP0543752A1 EP92420429A EP92420429A EP0543752A1 EP 0543752 A1 EP0543752 A1 EP 0543752A1 EP 92420429 A EP92420429 A EP 92420429A EP 92420429 A EP92420429 A EP 92420429A EP 0543752 A1 EP0543752 A1 EP 0543752A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- specific surface
- high specific
- carbide
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 39
- 150000001247 metal acetylides Chemical class 0.000 title claims description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 30
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000004913 activation Effects 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000003039 volatile agent Substances 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000011261 inert gas Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 238000010408 sweeping Methods 0.000 claims description 14
- 230000009471 action Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 239000011496 polyurethane foam Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 25
- 241000195940 Bryophyta Species 0.000 description 17
- 235000011929 mousse Nutrition 0.000 description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910003178 Mo2C Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241001080024 Telles Species 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000011872 intimate mixture Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 235000021183 entrée Nutrition 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B01J35/60—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
Definitions
- the invention relates to the technical field of silicon carbides or heavy metals with a large specific surface intended to serve as catalysts or catalyst supports for the chemical or petrochemical industry or for exhaust pipes.
- the specific surface of a catalyst is due to three types of porosity: a macroporosity due to pores with an average diameter greater than 2 ⁇ m, a mesoporosity due to pores with an average diameter of 30-50 angstroms and a microporosity due to pores of average diameter 5-15 angstroms.
- a catalyst must have sufficient macroporosity to give the gases to be treated access to the micro- and especially mesopores responsible for the catalytic activity proper.
- French patent application No. 2,645,143 describes a process for preparing heavy metal carbides with a large specific surface which consists in reacting a compound of the heavy metal under vacuum, at a temperature such that this compound is gaseous, on carbon having a large specific surface, for example activated carbon.
- the carbide obtained retains the memory of the specific surface of the starting carbon and has a specific surface clearly greater than that of the metal carbides of the prior art, although less than that of the starting carbon.
- the catalysts or supports obtained are in the form of powder, or agglomerates of granule type intended to constitute a fixed bed placed in a reactor.
- the gases to be treated circulate, sometimes at high speed through this bed and this results in attrition phenomena with the production of fines which plug the bed or seal the sintered parts which delimit the bed.
- the inventors posed the problem of obtaining carbides with a high specific surface in monolithic form and having a large open macroporosity allowing easy access to the reaction gases.
- the object of the invention is a process for the preparation of metal carbides with a high specific surface in monolithic form having a large open macroporosity allowing easy access to the reaction gases, characterized in that one starts with a carbon foam, which 'It is activated to increase its specific surface area and the activated foam is subjected, under inert gas sweeping or under vacuum, to the action of a volatile compound of the metal considered.
- a carbon foam which 'It is activated to increase its specific surface area and the activated foam is subjected, under inert gas sweeping or under vacuum, to the action of a volatile compound of the metal considered.
- a second object of the invention is a monolithic catalyst or catalyst support consisting of a foam of metallic carbide or silicon carbide having a large open macroporosity, a large specific surface due mainly to its mesoporosity and a small dimension of crystallites and containing no metal or other residual metallic compound.
- French patent application No. 2,645,143 cited above describes the principle of preparation of metal carbides with a large specific surface area as well as examples of implementation.
- the carbon with a large specific surface for example activated carbon
- the assembly placed in a crucible is then brought to a temperature of between 900 and 1400 ° C. under a vacuum of less than 13 hPa for a period of between 1 and 7 hours but most often of at least 4 hours.
- US Patent 2,431,326 (Heyroth) describes a product consisting of a continuous and crosslinked backbone of crystallized SiC uniformly distributed and the interstices of which are filled with silicon or a compound rich in silicon.
- the skeleton can be made by calcining wood, molasses, casein, dextrin, flour or other carbonizable substances.
- the reaction of ClH or SO4H2 is used on furfural, furfuryl alcohol or their mixtures: very quickly the carbon precipitates and grows in dendritic form to form a sponge filling the entire container.
- the skeleton thus obtained is brought into contact with silicon, for example by causing it to float on molten Si far above its melting point or by subjecting it to silicon vapors.
- Patent FR 1 484 116 (US Atomic Energy Commission) describes a process for the preparation of carbon foams and carbides (in particular Si) by a technique derived from the preparation of polyurethane foams.
- the reaction of an isocyanate on an alcohol or a phenol leads to a urethane and with diisocyanates and dialcohols, linear polyurethanes of formula are obtained: (-OC-NH-R-NH-CO-OR′-O-)
- isocyanates react with water to give CO2 and an ureine.
- Polymerization in the presence of water therefore makes it possible to form polyurethane foams which, by carbonization, give carbon foams.
- the carbon yield is low and the foams obtained are not solid.
- the carbide is obtained in a single operation, at the time of the calcination of the mixture of resins with the metal oxide or the metal, which does not make it possible to control the specific surface of the carbide obtained.
- Patent GB 2 137 974 (UK Atomic Energy Authority) describes the manufacture of a silicon matrix reinforced by a network of silicon carbide by treatment of a carbon foam by contacting molten silicon.
- Carbon foams are in the form of a three-dimensional network of kinds of interconnected cages whose edges have thicknesses of the order of a few micrometers, the length of these edges being able to vary from 50 to 500 micrometers.
- Their BET surface is very small: it is most often less than 1 m2 / g.
- Their density can vary in large proportions: from 0.03 to 0.1 g / cm3, depending on the relative dimensions of the thicknesses and lengths of the edges.
- foams of greater or lesser density are obtained by calcination of foams of organic resins, for example polyurethanes.
- Two precursors are particularly well suited to the intended use: polyacrylonitrile or PAN and polyurethane foams.
- the PAN used is in the form of rigid panels with a density of between 0.03 and 0.3 g / cm3, of the type sold for example by the company SAITEC. Its porous texture is essentially closed, but the Applicant has discovered that it is possible to manufacture, by pyrolysis, a carbon foam extremely rich in open micropores and mesopores. In order to develop a macroporosity sufficient to allow access of the gases to these meso- and micropores, it suffices to drill fine and closely spaced holes in the part having the geometry of the desired catalyst cut from the panel. The part is then pyrolyzed, at a temperature of 700-900 ° C., for 1 to 2 hours under a neutral atmosphere, nitrogen or argon, for example. The total specific surface of the carbon foam obtained is then greater than 300 m2 / g, that due to the mesopores being from 10 to 100 m2 / g. In these conditions, it is not necessary to activate the foam.
- Polyurethane foams have multiple applications in everyday life: packaging, furniture, etc ... It is therefore very easy to get them at low cost, by recovering used foam, for example.
- Carbon foams commercial or manufactured, do not exhibit, except those prepared from PAN, a meso- and microporosity sufficient to be used as catalysts. They should therefore be activated.
- This operation has the effect of developing, by gentle oxidation of the foam, a meso- and microporosity consisting of pores with diameters between 20 and 200 angstroms. Its specific surface thus goes from less than 1 m2 / g to several tens or even hundreds of m2 / g. It can be done batchwise by fixed loads or, preferably in a passage oven in which the foam parts are either placed on a conveyor belt or placed in containers which pass through the oven.
- the last step consists in exposing the activated foam part to the action of a volatile metal compound whose carbide is to be prepared at a temperature and for a duration such that the compound is reduced to metal, and that the metal either fueled.
- This step is carried out either under vacuum or under sweeping of inert gas at atmospheric pressure.
- the metals from which carbide is to be obtained by the process of the invention are in particular the transition metals (groups 3b, 4b, 5b, 6b, 7b, 8 of series 4, 5, 6 of the classification of elements), rare earth metals and actinides, but also the silicon. They must also have at least one volatile compound under the temperature conditions of the reaction.
- oxides or iodides are preferably chosen, but other compounds may also be suitable such as chlorides, fluorides or sublimable organometallic compounds.
- metals having these characteristics and whose carbides have a catalytic interest mention may be made of Mo, W, Re, V, Nb, Ta, Ti, Cr, Ni.
- the metallic compound can be in the form of a more or less fine powder, or in agglomerated form, granules or pellets for example.
- this sub-oxide SiO is unstable at low temperature where it undergoes a disproportionation into Si and SiO 2 according to the preceding reverse reaction.
- the Applicant has discovered that, in the case of carburetion under an inert gas sweep, the CO content at the outlet of the reactor constituted a means of controlling its operation to ensure optimum and constant yield and good product quality.
- the Applicant has shown during its research that all of the carbon monoxide present in the sweeping gas does not only come from reduction and carburation reactions, but also from the carbon foam itself.
- This foam produced at a temperature lower than that of the reactions involved in the present process, contains organic chemical species on the surface, consequently comprising hydrogen and oxygen atoms. When these organic products are brought to carburetion temperature, they decompose, giving off CO and OH2, which are harmful to carburetion reactions.
- One of the means of the invention therefore consists in carrying out a prior degassing of the carbon foam before bringing it into contact with the oxide of the metal from which it is desired to obtain the carbide.
- This degassing is carried out under primary vacuum or under the sweeping of an inert gas such as argon at a temperature and for a duration such that the carbon foam is then placed at a temperature and in a flow of inert gas identical to that of the carburetion reaction, the partial pressure of CO does not exceed, in the case of carburetion of silicon 2 hPa.
- the recommended degassing takes place at temperatures between 1000 and 1200 ° C for periods of 0.5 to 2 hours.
- the method therefore includes a regulation loop comprising the continuous measurement or at regular intervals of the CO content of the inert gas at the outlet of the reactor, the comparison with a set interval and a modification of the operating parameters for bring the CO content within this range. It is preferable to act on the flow of inert gas which will be increased if the CO content increases. To this end, an addition of inert gas is triggered if the CO content exceeds a certain threshold, for example at 2 hPa. On the contrary, when the CO pressure becomes lower than another threshold, for example 0.05 hPa, this additional flow of inert gas is eliminated. It is also possible to vary the reaction temperature, which is decreased or increased depending on whether the CO content increases or decreases, but this is more difficult to apply since the temperature variations have more inertia than the flow variations.
- the product according to the invention that is to say the catalyst or catalyst support obtained has characteristics which reflect its filiation from carbon foam activated.
- Its macroporosity thus consists of a three-dimensional network of kinds of interconnected cages whose edges have thicknesses of a few micrometers, the length of these edges being able to vary from 50 to 500 micrometers.
- the mesoporosity developed by the carbon foam activation treatment remains, but the mean diameter of the mesopores has increased by an approximate factor of 3.
- the microporosity developed by the carbon foam activation treatment has almost completely disappeared. This results in a BET surface area that is lower than that of the activated foam but higher than that of the starting carbon foam: it is between 20 and 100 m2 / g.
- the density of the carbide foam is of the same order as that of the carbon foam: from 0.03 to 0.1 g / cm3, depending on the relative dimensions of the thicknesses and the lengths of the edges.
- the carbide obtained consists of elementary or crystallite crystals of small dimensions, between 40 and 400 angstroms. It contains little or no residual metal, less than 0.1% by weight.
- Example 1 Manufacture of carbide foam from polyacrylonitrile.
- a piece having the shape of a cylinder with a diameter of 25 mm and a length of 75 mm was cut from a rigid panel of PAN.
- radial holes with a diameter of 1 mm and a center distance of 3 mm were drilled over the entire surface of the cylinder.
- the part was then pyrolyzed, at a temperature of 800 ° C., for 2 hours under a nitrogen atmosphere.
- the specific surface of the carbon foam obtained due to the micropores is then 320 m2 / g and that due to the mesopores of 40 m2 / g. There is no need in these conditions, to activate the foam.
- the carbon foam is then placed in a reactor on a bed consisting of an intimate mixture of silicon powder and silica.
- the reactor is placed under argon sweeping with a flow rate of 50 liters / hour, then heated to a temperature of 1400 ° C. This temperature is then maintained for 5 hours. After which, still under argon sweeping, the reactor is cooled to room temperature.
- the product obtained is a silicon carbide foam which is in the form of a porous texture whose macroporosity is formed by the holes drilled in the precursor, whose microporosity has practically disappeared and whose mesoporosity represents a specific surface of 35 m2 / g.
- the silicon carbide crystallites have small dimensions, between 40 and 400 angstroms.
- the product contains little or no residual metal, less than 0.1% by weight.
- the permeability of this carbide has been compared with that of a conventional catalyst support, made of cordierite, of the same shape and the same size. This is, in fact, a very important feature of use for the exhaust catalysts which must not cause too great a pressure drop in the flow at high flow rate of the exhaust gases.
- Example 2 Manufacture of carbon foam from polyurethane.
- the carbon foam thus obtained has a macroporosity sufficient for the access of the gases, but its mesoporosity and its microporosity are insufficient. It is therefore necessary to carry out its activation, under the conditions of example 3 below before proceeding to carburetion under the conditions of example 1.
- Example 3 Activation of the foam.
- the foam is placed in a reactor brought to a temperature of 900 ° C. in which carbon dioxide gas free of traces of oxygen is circulated, at the rate of 200 liters / hour, measured under normal conditions of temperature and pressure.
- the activation reaction lasts 2 hours, after which the foam is cooled to room temperature under circulation of inert gas.
- the activated foam obtained has a considerably increased BET specific surface area of 680 m2 / g.
- Example 4 Manufacture of SiC silicon carbide foam.
- a sample of the activated foam obtained according to the conditions of Example 3 is placed in a reactor on a bed consisting of an intimate mixture of silicon powder and silica.
- the reactor is placed under argon sweeping with a flow rate of 50 liters / hour, then heated to a temperature of 1400 ° C. This temperature is then maintained for 5 hours. After which, still under argon sweeping, the reactor is cooled to room temperature.
- the reaction is controlled by the partial pressure of CO in the purging gas at the outlet of the reactor: when this partial pressure exceeds 2 hPa, the flow of argon is increased; when this pressure drops below 0.05 hPa, this flow rate is reduced to its initial value.
- the silicon carbide foam is then treated with air at a temperature between 600 and 800 ° C to remove the rest of the activated foam which has not reacted.
- Example 5 Manufacture of molybdenum carbide foam Mo2C.
- a sample of the foam obtained according to the conditions of Example 1 is placed in a reactor on a bed consisting of molybdenum oxide MoO3.
- the reactor is placed under an argon sweep with a flow rate of 50 liters / hour, then heated to a temperature of 1300 ° C. This temperature is then maintained for 5 hours. After which, still under argon sweeping, the reactor is cooled to room temperature.
- Example 6 Comparison with silicon carbide prepared from activated carbon.
- the silicon carbide foam obtained according to the conditions of Example 4 was compared with SiC granules of dimensions between 1.25 and 2.5 mm prepared from activated carbon on the one hand according to the conditions of the French application 2,621,904, that is to say under a vacuum of 10 ⁇ 2 mm of mercury (1.333 Pa), on the other hand according to similar conditions in which the vacuum has been replaced by an argon sweep.
- the composition of the phases (4th column) is obviously given before this treatment.
Abstract
Description
L'invention concerne le domaine technique des carbures de silicium ou de métaux lourds à grande surface spécifique destinés à servir de catalyseurs ou de supports de catalyseurs pour l'industrie chimique ou pétrochimique ou pour les pots d'échappement.The invention relates to the technical field of silicon carbides or heavy metals with a large specific surface intended to serve as catalysts or catalyst supports for the chemical or petrochemical industry or for exhaust pipes.
La surface spécifique d'un catalyseur est due à trois types de porosité: une macroporosité due à des pores de diamètre moyen supérieur à 2 µm, une mésoporosité due à des pores de diamètre moyen 30-50 angströms et une microporosité due à des pores de diamètre moyen 5-15 angströms. Un catalyseur doit présenter une macroporosité suffisante pour donner aux gaz à traiter accès aux micro- et surtout mésopores responsables de l'activité catalytique proprement dite.The specific surface of a catalyst is due to three types of porosity: a macroporosity due to pores with an average diameter greater than 2 μm, a mesoporosity due to pores with an average diameter of 30-50 angstroms and a microporosity due to pores of average diameter 5-15 angstroms. A catalyst must have sufficient macroporosity to give the gases to be treated access to the micro- and especially mesopores responsible for the catalytic activity proper.
La demande de brevet français n° 2 645 143 décrit un procédé de préparation de carbures de métaux lourds à grande surface spécifique qui consiste à faire réagir sous vide un composé du métal lourd, à une température telle que ce composé soit gazeux, sur du carbone ayant une grande surface spécifique, par exemple du charbon actif. Le carbure obtenu conserve la mémoire de la surface spécifique du carbone de départ et présente une surface spécifique nettement supérieure à celle des carbures métalliques de l'art antérieur, bien que plus faible que celle du carbone de départ.
Dans ce procédé de préparation de carbures, les catalyseurs ou supports obtenus sont sous forme de poudre, ou d'agglomérés de type granulés destinés à constituer un lit fixe placé dans un réacteur. Les gaz à traiter circulent, parfois à grande vitesse au travers de ce lit et il en résulte des phénomènes d'attrition avec production de fines qui viennent colmater le lit ou obturer les pièces frittées qui délimitent le lit.French patent application No. 2,645,143 describes a process for preparing heavy metal carbides with a large specific surface which consists in reacting a compound of the heavy metal under vacuum, at a temperature such that this compound is gaseous, on carbon having a large specific surface, for example activated carbon. The carbide obtained retains the memory of the specific surface of the starting carbon and has a specific surface clearly greater than that of the metal carbides of the prior art, although less than that of the starting carbon.
In this process for the preparation of carbides, the catalysts or supports obtained are in the form of powder, or agglomerates of granule type intended to constitute a fixed bed placed in a reactor. The gases to be treated circulate, sometimes at high speed through this bed and this results in attrition phenomena with the production of fines which plug the bed or seal the sintered parts which delimit the bed.
Pour certaines applications catalytiques, en particulier pour la catalyse de l'oxydation des gaz d'échappement, on a besoin de choisir la géométrie du support ou du catalyseur et de le réaliser sous forme de pièces monolithiques, en assurant l'accessibilité du catalyseur aux gaz à traiter par sa macroporosité.For certain catalytic applications, in particular for the catalysis of the oxidation of exhaust gases, it is necessary to choose the geometry of the support or of the catalyst and to produce it in the form of monolithic parts, ensuring the accessibility of the catalyst to gas to be treated by its macroporosity.
Les inventeurs se sont posé le problème d'obtenir des carbures à haute surface spécifique sous forme monolithique et présentant une importante macroporosité ouverte permettant un accès facile aux gaz réactionnels.The inventors posed the problem of obtaining carbides with a high specific surface in monolithic form and having a large open macroporosity allowing easy access to the reaction gases.
Ainsi, alors que dans le procédé de la demande de brevet français n° 2 645 143, on fabrique d'abord le carbure et qu'on le dispose ensuite en lit, dans le procédé de l'invention, on fabrique d'abord un solide poreux de carbone que l'on transforme ensuite en carbure métallique.Thus, while in the process of French patent application No. 2,645,143, the carbide is first manufactured and then placed in a bed, in the process of the invention, a porous solid of carbon which is then transformed into metallic carbide.
L'objet de l'invention est un procédé de préparation de carbures métalliques à haute surface spécifique sous forme monolithique présentant une importante macroporosité ouverte permettant un accès facile aux gaz réactionnels caractérisé en ce que l'on part d'une mousse de carbone, qu'on l'active pour augmenter sa surface spécifique et qu'on soumet la mousse activée, sous balayage de gaz inerte ou sous vide, à l'action d'un composé volatil du métal considéré. L'utilisation de certains précurseurs organiques permettant par calcination d'obtenir des mousses de carbone présentant des caractéristiques interessantes fait également partie de l'invention.The object of the invention is a process for the preparation of metal carbides with a high specific surface in monolithic form having a large open macroporosity allowing easy access to the reaction gases, characterized in that one starts with a carbon foam, which 'It is activated to increase its specific surface area and the activated foam is subjected, under inert gas sweeping or under vacuum, to the action of a volatile compound of the metal considered. The use of certain organic precursors making it possible by calcination to obtain carbon foams having interesting characteristics is also part of the invention.
Un deuxième objet de l'invention est un catalyseur ou support de catalyseur monolithique constitué d'une mousse de carbure métallique ou de carbure de silicium présentant une importante macroporosité ouverte, une grande surface spécifique due surtout à sa mésoporosité et une faible dimension de cristallites et ne comportant ni métal ni autre composé métallique résiduels.A second object of the invention is a monolithic catalyst or catalyst support consisting of a foam of metallic carbide or silicon carbide having a large open macroporosity, a large specific surface due mainly to its mesoporosity and a small dimension of crystallites and containing no metal or other residual metallic compound.
La demande de brevet français n° 2 645 143 citée ci-dessus décrit le principe de préparation des carbures métalliques à grande surface spécifique ainsi que des exemples de mise en oeuvre. On mélange le carbone à grande surface spécifique, par exemple du charbon actif avec un composé, volatil à la température de réaction, du métal dont on veut obtenir le carbure. L'ensemble placé dans un creuset est ensuite porté à une température comprise entre 900 et 1400°C sous un vide inférieur à 13 hPa pendant une durée comprise entre 1 et 7 heures mais le plus souvent d'au moins 4 heures.
En variante, il est également possible de vaporiser le composé volatil du métal dans une première zone et d'opérer la réduction et la carburation dans une deuxième zone, les températures des deux zones pouvant être différentes.French patent application No. 2,645,143 cited above describes the principle of preparation of metal carbides with a large specific surface area as well as examples of implementation. The carbon with a large specific surface, for example activated carbon, is mixed with a compound, volatile at the reaction temperature, of the metal from which the carbide is to be obtained. The assembly placed in a crucible is then brought to a temperature of between 900 and 1400 ° C. under a vacuum of less than 13 hPa for a period of between 1 and 7 hours but most often of at least 4 hours.
As a variant, it is also possible to vaporize the volatile compound from the metal in a first zone and to carry out the reduction and the carburetion in a second zone, the temperatures of the two zones possibly being different.
La demande de brevet français FR 2 621 904 décrit la préparation de carbure de silicium SiC à surface spécifique supérieure à 100 m2/g par:
- génération dans une première zone, de vapeur de SiO par réaction de SiO2 sur Si à une température comprise entre 1100 et 1400°C, sous un vide de 0,1 à 1,5 hPa;
- réaction, dans une deuxième zone, du SiO formé avec du carbone à surface spécifique supérieure à 200 m2/g, à une température comprise entre 1100 et 1400°C.
- generation in a first zone, of SiO vapor by reaction of SiO2 on Si at a temperature between 1100 and 1400 ° C, under a vacuum of 0.1 to 1.5 hPa;
- reaction, in a second zone, of SiO formed with carbon with a specific surface greater than 200 m2 / g, to a temperature between 1100 and 1400 ° C.
Le brevet US 2 431 326 (Heyroth) décrit un produit constitué d'un squelette continu et réticulé de SiC cristallisé réparti de façon uniforme et dont les interstices sont remplis de silicium ou d'un composé riche en silicium.
Le squelette peut être fait par calcination de bois, de mélasses, de caséine, de dextrine, de farines ou d'autres substances carbonisables. De préférence, on utilise la réaction de ClH ou de SO4H2 sur du furfural, de l'alcool furfurylique ou leurs mélanges: très rapidement le carbone précipite et croît sous forme dendritique pour former une éponge remplissant tout le récipient.
Le squelette ainsi obtenu est mis en contact avec du silicium, par exemple en le faisant flotter sur du Si fondu très au-dessus de son point de fusion ou en le soumettant à des vapeurs de silicium.US Patent 2,431,326 (Heyroth) describes a product consisting of a continuous and crosslinked backbone of crystallized SiC uniformly distributed and the interstices of which are filled with silicon or a compound rich in silicon.
The skeleton can be made by calcining wood, molasses, casein, dextrin, flour or other carbonizable substances. Preferably, the reaction of ClH or SO4H2 is used on furfural, furfuryl alcohol or their mixtures: very quickly the carbon precipitates and grows in dendritic form to form a sponge filling the entire container.
The skeleton thus obtained is brought into contact with silicon, for example by causing it to float on molten Si far above its melting point or by subjecting it to silicon vapors.
Le brevet FR 1 484 116 (US Atomic Energy Commission ) décrit un procédé de préparation de mousses de carbone et de carbures (en particulier de Si) par une technique dérivée de la préparation de mousses de polyuréthannes.
La réaction d'un isocyanate sur un alcool ou un phénol conduit à un uréthanne et avec des diisocyanates et des dialcools on obtient des polyuréthannes linéaires de formule:
( -OC-NH-R-NH-CO-O-R′-O-)
Patent FR 1 484 116 (US Atomic Energy Commission) describes a process for the preparation of carbon foams and carbides (in particular Si) by a technique derived from the preparation of polyurethane foams.
The reaction of an isocyanate on an alcohol or a phenol leads to a urethane and with diisocyanates and dialcohols, linear polyurethanes of formula are obtained:
(-OC-NH-R-NH-CO-OR′-O-)
Par ailleurs, les isocyanates réagissent avec l'eau en donnant du CO2 et une uréine.In addition, isocyanates react with water to give CO2 and an ureine.
La polymérisation en présence d'eau permet donc de former des mousses de polyuréthannes qui, par carbonisation donnent des mousses de carbone. Mais le rendement carbone est faible et les mousses obtenues ne sont pas solides.Polymerization in the presence of water therefore makes it possible to form polyurethane foams which, by carbonization, give carbon foams. However, the carbon yield is low and the foams obtained are not solid.
L'invention de ce brevet consiste donc:
- d'une part à mélanger un liant dont le rendement en C est élevé: de l'alcool furfurylique partiellement polymérisé,
- d'autre part à mélanger des poudres de métaux ou d'oxydes métalliques pour obtenir des mousses métalliques ou de carbures métalliques ( W, Ta, Nb, Al, B, Si ).
- on the one hand, to mix a binder with a high C yield: partially polymerized furfuryl alcohol,
- on the other hand to mix powders of metals or metal oxides to obtain metallic foams or metallic carbides (W, Ta, Nb, Al, B, Si).
Dans le procédé décrit, l'obtention du carbure se fait en une seule opération, au moment de la calcination du mélange des résines avec l'oxyde métallique ou le métal, ce qui ne permet pas de maîtriser la surface spécifique du carbure obtenu. Dans le procédé de la présente demande de brevet, au contraire, l'obtention du carbure se fait en deux temps séparés par l'activation de la mousse qui permet d'atteindre une surface spécifique du carbure beaucoup plus élevée (20 à 100 m²/g), une dimension des cristallites plus faible (40 à 400 angströms = 40 à 400.10⁻¹⁰ m ) et une mousse de carbure ne contenant que peu ou pas de métal résiduel (<0,1 % en poids).In the process described, the carbide is obtained in a single operation, at the time of the calcination of the mixture of resins with the metal oxide or the metal, which does not make it possible to control the specific surface of the carbide obtained. In the process of the present patent application, on the contrary, the carbide is obtained in two separate stages by the activation of the foam which makes it possible to reach a much higher specific surface of the carbide (20 to 100 m² / g), a smaller crystallite dimension (40 to 400 angstroms = 40 to 400.10⁻¹⁰ m) and a carbide foam containing little or no residual metal (<0.1% by weight).
Le brevet GB 2 137 974 (UK Atomic Energy Authority) décrit la fabrication d'une matrice de silicium renforcée par un réseau de carbure de silicium par traitement d'une mousse de carbone par mise au contact de silicium fondu.Patent GB 2 137 974 (UK Atomic Energy Authority) describes the manufacture of a silicon matrix reinforced by a network of silicon carbide by treatment of a carbon foam by contacting molten silicon.
Le procédé de l'invention consiste en la combinaison des étapes successives suivantes:
- de façon facultative, préparer de la mousse de carbone par calcination d'une mousse d'un polymère organique;
- fabriquer, à partir de la mousse de carbone ainsi préparée ou d'une mousse de carbone du commerce une pièce ayant les dimensions et la forme du support de catalyseur ou du catalyseur que l'on veut obtenir;
- de préférence, dégazer la pièce en mousse de carbone sous vide ou sous balayage d'un gaz inerte tel l'argon;
- activer la surface de cette pièce en l'exposant à une oxydation ménagée par le dioxyde de carbone CO2;
- exposer la pièce ainsi activée à l'action d'un composé volatil du métal dont on veut préparer le carbure à une température (1000 à 1400°C) et pendant une durée (2 à 6 heures) telles que le composé soit réduit en métal, et que le métal soit carburé. Cette étape est conduite soit sous vide, soit sous balayage de gaz inerte à la pression atmosphérique.
- optionally, preparing carbon foam by calcining a foam of an organic polymer;
- manufacture, from the carbon foam thus prepared or from a commercial carbon foam, a part having the dimensions and the shape of the catalyst support or of the catalyst that it is desired to obtain;
- preferably degas the carbon foam part under vacuum or under sweeping of an inert gas such as argon;
- activate the surface of this part by exposing it to mild oxidation by carbon dioxide CO2;
- expose the part thus activated to the action of a volatile compound of the metal whose carbide is to be prepared at a temperature (1000 to 1400 ° C) and for a period (2 to 6 hours) such that the compound is reduced to metal , and that the metal is carburetted. This step is carried out either under vacuum or under sweeping of inert gas at atmospheric pressure.
Les mousses de carbone se présentent sous la forme d'un réseau tridimensionnel de sortes de cages interconnectées dont les arêtes ont des épaisseurs de l'ordre de quelques micromètres, la longueur de ces arêtes pouvant varier de 50 à 500 micromètres. Leur surface BET est très faible: elle est le plus souvent inférieure à 1 m²/g. Leur masse volumique peut varier dans de grandes proportions: de 0,03 à 0,1 g/ cm³, selon les dimensions relatives des épaisseurs et des longueurs des arêtes. Selon la nature de la réaction catalytique et selon les caractéristiques mécaniques ou thermiques que l'on attend du catalyseur ou de son support, on sera amené à choisir des mousses de masse volumique plus ou moins importante. Elles sont obtenues par calcination de mousses de résines organiques, par exemple polyuréthannes.Carbon foams are in the form of a three-dimensional network of kinds of interconnected cages whose edges have thicknesses of the order of a few micrometers, the length of these edges being able to vary from 50 to 500 micrometers. Their BET surface is very small: it is most often less than 1 m² / g. Their density can vary in large proportions: from 0.03 to 0.1 g / cm³, depending on the relative dimensions of the thicknesses and lengths of the edges. Depending on the nature of the catalytic reaction and on the mechanical or thermal characteristics expected from the catalyst or its support, it will be necessary to choose foams of greater or lesser density. They are obtained by calcination of foams of organic resins, for example polyurethanes.
Il est possible de se les procurer dans le commerce. Cependant, la demanderesse a trouvé qu'il était avantageux de les préparer à partir de certains précurseurs organiques, des mousses de polymères, en vue d'obtenir une texture poreuse favorable à leur utilisation comme support de catalyseurs ou catalyseurs.It is possible to obtain them commercially. However, the applicant has found that it was advantageous to prepare them from certain organic precursors, polymer foams, with a view to obtaining a porous texture favorable to their use as a support for catalysts or catalysts.
Deux précurseurs se révèlent particulièrement bien adaptés à l'utilisation envisagée: le polyacrylonitrile ou PAN et les mousses de polyuréthannes.Two precursors are particularly well suited to the intended use: polyacrylonitrile or PAN and polyurethane foams.
Le PAN utilisé se présente sous la forme de panneaux rigides de masse volumique comprise entre 0,03 et 0,3 g/cm3, du type commercialisé par exemple par la Société SAITEC. Sa texture poreuse est essentiellement fermée, mais la demanderesse a découvert qu'il était possible de fabriquer, par pyrolyse, une mousse de carbone extrêmement riche en micropores et mésopores ouverts. Afin de développer une macroporosité suffisante pour permettre l'accès des gaz à ces méso- et micropores, il suffit de percer des trous fins et rapprochés dans la pièce ayant la géométrie du catalyseur souhaité découpée dans le panneau. On procède alors à la pyrolyse de la pièce, à une température de 700-900°C, pendant 1 à 2 heures sous atmosphère neutre, azote ou argon, par exemple. La surface spécifique totale de la mousse de carbone obtenue est alors supérieure à 300 m2/g, celle due aux mésopores étant de 10 à 100 m2/g. Il n'est pas nécessaire, dans ces conditions, de procéder à une activation de la mousse.The PAN used is in the form of rigid panels with a density of between 0.03 and 0.3 g / cm3, of the type sold for example by the company SAITEC. Its porous texture is essentially closed, but the Applicant has discovered that it is possible to manufacture, by pyrolysis, a carbon foam extremely rich in open micropores and mesopores. In order to develop a macroporosity sufficient to allow access of the gases to these meso- and micropores, it suffices to drill fine and closely spaced holes in the part having the geometry of the desired catalyst cut from the panel. The part is then pyrolyzed, at a temperature of 700-900 ° C., for 1 to 2 hours under a neutral atmosphere, nitrogen or argon, for example. The total specific surface of the carbon foam obtained is then greater than 300 m2 / g, that due to the mesopores being from 10 to 100 m2 / g. In these conditions, it is not necessary to activate the foam.
Les mousses de polyuréthannes ont de multiples applications dans la vie courante: emballage, ameublement, etc...Il est donc très facile de se les procurer à bas prix, en récupérant des mousses usagées, par exemple.Polyurethane foams have multiple applications in everyday life: packaging, furniture, etc ... It is therefore very easy to get them at low cost, by recovering used foam, for example.
La fabrication de mousses de carbone à partir de ces mousses comporte les étapes suivantes:
- découpage d'une pièce ayant la forme du support de catalyseur souhaitée;
- lavage de la mousse par une solution chaude de soude pendant quelques minutes;
- rinçage à l'eau courante et séchage;
- imprégnation de la mousse avec une résine, par exemple furfurylique et essorage de la mousse imprégnée de façon à ce qu'il reste de 0,03 à 0,1 g de résine /cm3 de mousse;
- pyrolyse de la mousse imprégnée jusque 1200°C.
- cutting of a part having the shape of the desired catalyst support;
- washing the foam with a hot soda solution for a few minutes;
- rinsing with running water and drying;
- impregnating the foam with a resin, for example furfuryl and wringing out the impregnated foam so that there remains from 0.03 to 0.1 g of resin / cm 3 of foam;
- pyrolysis of the impregnated foam up to 1200 ° C.
Ce mode opératoire permet d'élaborer des mousses de carbone ayant une bonne résistance à l'effritement et une structure homogène.This procedure makes it possible to develop carbon foams having good resistance to crumbling and a homogeneous structure.
Les mousses de carbone, du commerce ou fabriquées, ne présentent pas, sauf celles préparées à partir de PAN, une méso- et microporosité suffisantes pour être utilisées comme catalyseurs. Il convient donc de les activer.Carbon foams, commercial or manufactured, do not exhibit, except those prepared from PAN, a meso- and microporosity sufficient to be used as catalysts. They should therefore be activated.
Pour activer la mousse, on la chauffe à une température comprise entre 700°C et 1000°C, sous balayage de gaz carbonique CO2 à la pression atmosphérique, pendant une durée de 1 à 24 heures.To activate the foam, it is heated to a temperature between 700 ° C and 1000 ° C, under a sweep of carbon dioxide CO2 at atmospheric pressure, for a period of 1 to 24 hours.
Cette opération a pour effet de développer par oxydation ménagée de la mousse une méso- et microporosité constituées de pores de diamètres compris entre 20 et 200 angströms. Sa surface spécifique passe ainsi de moins de 1 m²/g à plusieurs dizaines voire plusieurs centaines de m²/g. Elle peut se faire en discontinu par charges fixes ou, de préférence dans un four à passage dans lequel les pièces en mousse sont soit placés sur une bande transporteuse soit placés dans des récipients qui traversent le four.This operation has the effect of developing, by gentle oxidation of the foam, a meso- and microporosity consisting of pores with diameters between 20 and 200 angstroms. Its specific surface thus goes from less than 1 m² / g to several tens or even hundreds of m² / g. It can be done batchwise by fixed loads or, preferably in a passage oven in which the foam parts are either placed on a conveyor belt or placed in containers which pass through the oven.
Enfin, la dernière étape consiste à exposer la pièce en mousse activée à l'action d'un composé volatil du métal dont on veut préparer le carbure à une température et pendant une durée telles que le composé soit réduit en métal, et que le métal soit carburé. Cette étape est réalisée soit sous vide, soit sous balayage de gaz inerte à la pression atmosphérique. Les métaux dont on veut obtenir le carbure par le procédé de l'invention sont en particulier les métaux de transition, (groupes 3b, 4b, 5b, 6b, 7b, 8 des séries 4, 5, 6 de la classification des éléments), les métaux des terres rares et les actinides, mais également le silicium.
Ils doivent avoir, en outre, au moins un composé volatil dans les conditions de température de la réaction. Parmi ces composés, on choisit de préférence les oxydes ou les iodures, mais d'autres composés peuvent aussi convenir tels les chlorures, fluorures ou des composés organométalliques sublimables. Parmi les métaux présentant ces caractéristiques et dont les carbures ont un interêt catalytique, on peut citer Mo, W, Re, V, Nb, Ta, Ti, Cr, Ni.Finally, the last step consists in exposing the activated foam part to the action of a volatile metal compound whose carbide is to be prepared at a temperature and for a duration such that the compound is reduced to metal, and that the metal either fueled. This step is carried out either under vacuum or under sweeping of inert gas at atmospheric pressure. The metals from which carbide is to be obtained by the process of the invention are in particular the transition metals (groups 3b, 4b, 5b, 6b, 7b, 8 of series 4, 5, 6 of the classification of elements), rare earth metals and actinides, but also the silicon.
They must also have at least one volatile compound under the temperature conditions of the reaction. Among these compounds, oxides or iodides are preferably chosen, but other compounds may also be suitable such as chlorides, fluorides or sublimable organometallic compounds. Among the metals having these characteristics and whose carbides have a catalytic interest, mention may be made of Mo, W, Re, V, Nb, Ta, Ti, Cr, Ni.
Pour exposer la mousse activée à l'action du composé métallique volatil, plusieurs méthodes sont possibles:
- on peut tout d'abord, comme pour l'opération précédente d'activation, opérer en discontinu en immergeant ou en posant simplement la pièce en mousse activée dans ou sur un lit de poudre du composé volatil. L'ensemble est alors placé dans une enceinte portée à la température voulue, comprise entre 1000 et 1400°C. L'application du vide ou un balayage par un gaz inerte favorise l'élimination du monoxyde de carbone CO qui se forme lorsque le composé volatil choisi est un oxyde.
- cette étape pouvant être réalisée sous balayage de gaz inerte à pression atmosphérique, on peut aussi, comme dans l'opération d'activation, travailler en continu, dans un four à passage. Les pièces de mousse activée sont toujours immergées ou posées simplement dans ou sur un lit de poudre du composé volatil. L'ensemble est placé dans des récipients successifs qui traversent le four chauffé à la température voulue et balayé par un gaz inerte.
- we can first of all, as for the previous activation operation, operate batchwise by immersing or simply placing the activated foam part in or on a bed of powder of the volatile compound. The assembly is then placed in an enclosure brought to the desired temperature, between 1000 and 1400 ° C. The application of vacuum or sweeping with an inert gas promotes the elimination of the carbon monoxide CO which forms when the volatile compound chosen is an oxide.
- this step being able to be carried out under sweeping of inert gas at atmospheric pressure, it is also possible, as in the activation operation, to work continuously, in a passage oven. The activated foam pieces are always submerged or simply placed in or on a bed of volatile compound powder. The assembly is placed in successive containers which pass through the oven heated to the desired temperature and swept by an inert gas.
Le composé métallique peut être sous forme de poudre plus ou moins fine, ou sous forme agglomérée, granulés ou boulettes par exemple.The metallic compound can be in the form of a more or less fine powder, or in agglomerated form, granules or pellets for example.
Dans le cas particulier du silicium, il est avantageux d'utiliser comme composé volatil le sous-oxyde de silicium SiO. Ce composé volatil s'obtient par réduction de la silice SiO2 soit par le carbone, soit par le silicium, suivant l'une ou l'autre des réactions:
SiO2 + C = SiO + CO
SiO2 + Si = 2SiO
In the particular case of silicon, it is advantageous to use as silicon volatile compound SiO. This volatile compound is obtained by reduction of the silica SiO2 either by carbon or by silicon, according to one or other of the reactions:
SiO2 + C = SiO + CO
SiO2 + Si = 2SiO
Mais ce sous-oxyde SiO est instable à basse température où il subit une dismutation en Si et SiO2 selon la réaction précédente inversée. Aussi, lorsque l'on veut préparer du carbure de silicium selon la présente invention, faut-il fabriquer le SiO dans le four de carburation lui-même. Cela se fait de façon très simple: on procèdera comme dans le cas général décrit ci-dessus, mais on remplacera le lit de composé volatil par un lit de silice mélangée à du silicium. La réaction de transformation en SiC est rapide et complète.However, this sub-oxide SiO is unstable at low temperature where it undergoes a disproportionation into Si and SiO 2 according to the preceding reverse reaction. Also, when it is desired to prepare silicon carbide according to the present invention, it is necessary to manufacture the SiO in the carburetion furnace itself. This is done in a very simple way: we will proceed as in the general case described above, but we will replace the volatile compound bed with a bed of silica mixed with silicon. The reaction for transformation into SiC is rapid and complete.
La demanderesse a découvert que, dans le cas de carburation sous balayage de gaz inerte, la teneur en CO à la sortie du réacteur constituait un moyen de piloter son fonctionnement pour assurer un rendement optimal et constant et une bonne qualité des produits.The Applicant has discovered that, in the case of carburetion under an inert gas sweep, the CO content at the outlet of the reactor constituted a means of controlling its operation to ensure optimum and constant yield and good product quality.
Les réactions de réduction et de carburation produisent du CO qui est entrainé par le gaz inerte, ce qui favorise l'évolution de la réaction vers la formation du carbure. Les inventeurs ont découvert le rôle important de la pression partielle de CO dans le gaz inerte. Si cette pression devient trop élevée, elle a deux effets nocifs:
- elle peut localement, en fonction de la température donner lieu à une rétrogradation de la réaction de carburation, le CO réagissant sur le carbure formé pour redonner de l'oxyde et du carbone, ce qui diminue d'autant le rendement du réacteur;
- elle peut donner lieu à l'oxydation de l'oxyde volatil pour former un oxyde moins volatil en générant des fines de carbone. C'est le cas, en particulier, de l'oxyde de silicium SiO qui réagit sur le CO pour redonner de la silice et du carbone. Ce dépôt de carbone sur la source de SiO (mélange de Si et de SiO2) pollue ce mélange et donne naissance à du carbure qui n'a évidemment pas les caractéristiques, notamment de surface spécifique de celui obtenu par "filiation" à partir de carbone solide introduit comme matière première. La teneur en CO à la sortie du réacteur constitue donc un moyen de piloter son fonctionnement pour assurer un rendement optimal et constant et une bonne qualité des produits, en particulier un très faible taux d'oxyde n'ayant pas réagi.
- it can locally, as a function of the temperature, give rise to a demotion of the carburetion reaction, the CO reacting on the carbide formed to give back oxide and carbon, which decreases the reactor performance;
- it can give rise to the oxidation of the volatile oxide to form a less volatile oxide by generating carbon fines. This is the case, in particular, of silicon oxide SiO which reacts on CO to restore silica and carbon. This carbon deposition on the source of SiO (mixture of Si and SiO2) pollutes this mixture and gives rise to carbide which obviously does not have the characteristics, in particular of specific surface of that obtained by "filiation" from carbon. solid introduced as raw material. The CO content at the outlet of the reactor therefore constitutes a means of controlling its operation to ensure an optimal and constant yield and good quality of the products, in particular a very low level of unreacted oxide.
Cette découverte a conduit les inventeurs à introduire dans leur mode opératoire deux moyens supplémentaires: le dégazage préalable de la mousse de carbone et le pilotage de la réaction par la pression partielle de CO.This discovery led the inventors to introduce into their operating mode two additional means: the prior degassing of the carbon foam and the control of the reaction by the partial pressure of CO.
La demanderesse a montré au cours de ses recherches que la totalité de l'oxyde de carbone présent dans le gaz de balayage ne provient pas uniquement des réactions de réduction et de carburation, mais également de la mousse de carbone elle-même. Cette mousse, élaborée à une température inférieure à celles des réactions mises en jeu dans le présent procédé, contient en surface des espèces chimiques organiques comprenant par conséquent des atomes d'hydrogène et d'oxygène. Ces produits organiques, lorsqu'ils sont portés à la température de carburation se décomposent en donnant naissance à des dégagements de CO et de OH2, néfastes aux réactions de carburation.
L'un des moyens de l'invention consiste donc à procéder à un dégazage préalable de la mousse de carbone avant de la mettre en contact avec l'oxyde du métal dont on veut obtenir le carbure. Ce dégazage se fait sous vide primaire ou sous balayage d'un gaz inerte tel l'argon à une température et pendant une durée telles que, la mousse de carbone placée ensuite à une température et dans un débit de gaz inerte identiques à celle de la réaction de carburation, la pression partielle de CO n'excède pas, dans le cas de la carburation du silicium 2 hPa. Cette pression partielle correspond en effet sensiblement à la pression au-delà de laquelle, la réaction SiO + CO = SiO2 + C se produit dans le sens de la formation de SiO2.
Pratiquement, le dégazage recommandé se fait à des températures comprises entre 1000 et 1200°C pendant des durées de 0,5 à 2 heures.The Applicant has shown during its research that all of the carbon monoxide present in the sweeping gas does not only come from reduction and carburation reactions, but also from the carbon foam itself. This foam, produced at a temperature lower than that of the reactions involved in the present process, contains organic chemical species on the surface, consequently comprising hydrogen and oxygen atoms. When these organic products are brought to carburetion temperature, they decompose, giving off CO and OH2, which are harmful to carburetion reactions.
One of the means of the invention therefore consists in carrying out a prior degassing of the carbon foam before bringing it into contact with the oxide of the metal from which it is desired to obtain the carbide. This degassing is carried out under primary vacuum or under the sweeping of an inert gas such as argon at a temperature and for a duration such that the carbon foam is then placed at a temperature and in a flow of inert gas identical to that of the carburetion reaction, the partial pressure of CO does not exceed, in the case of carburetion of silicon 2 hPa. This partial pressure in fact corresponds substantially to the pressure above which the reaction SiO + CO = SiO2 + C occurs in the direction of the formation of SiO2.
In practice, the recommended degassing takes place at temperatures between 1000 and 1200 ° C for periods of 0.5 to 2 hours.
Pour permettre ce pilotage, le procédé comporte donc une boucle de régulation comprenant la mesure en continu ou à intervalles réguliers de la teneur en CO du gaz inerte à la sortie du réacteur, la comparaison avec un intervalle de consigne et une modification des paramètres opératoires pour ramener la teneur en CO à l'intérieur de cet intervalle. On agit de préférence sur le débit de gaz inerte que l'on augmentera si la teneur en CO augmente. A cet effet, une addition de gaz inerte est déclenchée si la teneur en CO dépasse un certain seuil fixé, par exemple à 2 hPa. Au contraire, lorsque la pression de CO devient inférieure à un autre seuil, par exemple 0,05 hPa, ce débit additionnel de gaz inerte est supprimé.
Il est aussi possible de faire varier température de réaction que l'on diminue ou augmente suivant que la teneur en CO augmente ou diminue, mais cela est plus difficilement applicable car les variations de températures présentent plus d'inertie que les variations de débit.To allow this control, the method therefore includes a regulation loop comprising the continuous measurement or at regular intervals of the CO content of the inert gas at the outlet of the reactor, the comparison with a set interval and a modification of the operating parameters for bring the CO content within this range. It is preferable to act on the flow of inert gas which will be increased if the CO content increases. To this end, an addition of inert gas is triggered if the CO content exceeds a certain threshold, for example at 2 hPa. On the contrary, when the CO pressure becomes lower than another threshold, for example 0.05 hPa, this additional flow of inert gas is eliminated.
It is also possible to vary the reaction temperature, which is decreased or increased depending on whether the CO content increases or decreases, but this is more difficult to apply since the temperature variations have more inertia than the flow variations.
Le procédé, incluant le pilotage du réacteur par la teneur en CO, est alors caractérisé par les étapes suivantes:
- introduire dans un réacteur un mélange réactif constitué d'une part de mousse de carbone dont la surface spécifique est au moins égale à 200 m²/g, et préalablement dégazé, d'autre part un composé, volatil dans les conditions de la réaction, du métal dont on fabrique le carbure, dans des proportions voisines de la stoechiométrie;
- balayer le réacteur par un courant de gaz inerte introduit du côté de l'entrée du mélange réactif et extrait du côté de la sortie du carbure obtenu;
- porter le mélange réactif à une température comprise entre 900 et 1400°C pendant un temps suffisant pour volatiliser le composé métallique, le réduire par le carbone et finalement carburer le produit réduit;
- refroidir le carbure obtenu, toujours en présence de gaz inerte, est refroidi jusqu'à une température telle qu'il ne s'oxyde plus au contact de l'air;
- extraire le carbure du réacteur.
et par le fait que l'on mesure en continu ou à intervalles réguliers la teneur en CO du gaz inerte à la sortie du réacteur, que l'on compare cette valeur à un interval de consigne et que l'on modifie les paramètres opératoires pour ramener la teneur en CO à l'intérieur de cet intervalle en agissant sur le débit de gaz inerte que l'on augmente si la teneur en CO augmente et que l'on diminue si la teneur en CO diminue ou sur la température de réaction.The process, including controlling the reactor by the CO content, is then characterized by the following stages:
- introducing into a reactor a reactive mixture consisting on the one hand of carbon foam whose specific surface is at least equal to 200 m² / g, and previously degassed, on the other hand a compound, volatile under the conditions of the reaction, metal from which the carbide is made, in proportions close to stoichiometry;
- sweep the reactor with a stream of inert gas introduced on the inlet side of the reactive mixture and extracted on the outlet side of the carbide obtained;
- bring the reactive mixture to a temperature between 900 and 1400 ° C for a time sufficient to volatilize the metal compound, reduce it with carbon and finally carburize the reduced product;
- cooling the carbide obtained, still in the presence of inert gas, is cooled to a temperature such that it no longer oxidizes on contact with air;
- extract the carbide from the reactor.
and by the fact that the CO content of the inert gas leaving the reactor is measured continuously or at regular intervals, that this value is compared to a set interval and that the operating parameters are modified to reduce the CO content within this range by acting on the inert gas flow rate which is increased if the CO content increases and which is decreased if the CO content decreases or on the reaction temperature.
Le produit selon l'invention, c'est-à-dire le catalyseur ou support de catalyseur obtenu présente des caractéristiques qui traduisent sa filiation à partir de la mousse de carbone activée.
Sa macroporosité est ainsi constituée d'un réseau tridimensionnel de sortes de cages interconnectées dont les arêtes ont des épaisseurs de quelques micromètres, la longueur de ces arêtes pouvant varier de 50 à 500 micromètres.
La mésoporosité développée par le traitement d'activation de la mousse de carbone subsiste, mais le diamètre moyen des mésopores a augmenté d'un facteur approximatif de 3.
La microporosité développée par le traitement d'activation de la mousse de carbone a disparu presque complètement. Il en résulte une surface BET plus faible que celle de la mousse activée mais plus élevée que celle de la mousse de carbone de départ: elle est comprise entre 20 et 100 m²/g.
La masse volumique de la mousse de carbure est du même ordre que celle de la mousse de carbone: de 0,03 à 0,1 g/ cm³, selon les dimensions relatives des épaisseurs et des longueurs des arêtes. Le carbure obtenu est constitué de cristaux élémentaires ou cristallites de faibles dimensions, comprises entre 40 et 400 angströms. Il ne contient que peu ou pas de métal résiduel, moins de 0,1 % en poids.The product according to the invention, that is to say the catalyst or catalyst support obtained has characteristics which reflect its filiation from carbon foam activated.
Its macroporosity thus consists of a three-dimensional network of kinds of interconnected cages whose edges have thicknesses of a few micrometers, the length of these edges being able to vary from 50 to 500 micrometers.
The mesoporosity developed by the carbon foam activation treatment remains, but the mean diameter of the mesopores has increased by an approximate factor of 3.
The microporosity developed by the carbon foam activation treatment has almost completely disappeared. This results in a BET surface area that is lower than that of the activated foam but higher than that of the starting carbon foam: it is between 20 and 100 m² / g.
The density of the carbide foam is of the same order as that of the carbon foam: from 0.03 to 0.1 g / cm³, depending on the relative dimensions of the thicknesses and the lengths of the edges. The carbide obtained consists of elementary or crystallite crystals of small dimensions, between 40 and 400 angstroms. It contains little or no residual metal, less than 0.1% by weight.
On a découpé dans un panneau rigide de PAN une pièce ayant la forme dun cylindre de diamètre 25 mm et de longueur 75 mm. Afin de développer une macroporosité suffisante pour permettre l'accès des gaz aux méso- et micropores qui vont être développés par calcination, on a percé des trous radiaux de diamètre 1 mm et d'entraxe 3 mm sur toute la surface du cylindre. On a procédé ensuite à la pyrolyse de la pièce, à une température de 800°C, pendant 2 heures sous atmosphère d'azote. La surface spécifique de la mousse de carbone obtenue due aux micropores est alors de 320 m2/g et celle due aux mésopores de 40 m2/g. Il n'est pas nécessaire, dans ces conditions, de procéder à une activation de la mousse.A piece having the shape of a cylinder with a diameter of 25 mm and a length of 75 mm was cut from a rigid panel of PAN. In order to develop a macroporosity sufficient to allow access of the gases to the meso- and micropores which will be developed by calcination, radial holes with a diameter of 1 mm and a center distance of 3 mm were drilled over the entire surface of the cylinder. The part was then pyrolyzed, at a temperature of 800 ° C., for 2 hours under a nitrogen atmosphere. The specific surface of the carbon foam obtained due to the micropores is then 320 m2 / g and that due to the mesopores of 40 m2 / g. There is no need in these conditions, to activate the foam.
La mousse de carbone est alors placée dans un réacteur sur un lit constitué d'un mélange intime de poudre de silicium et de silice. Le réacteur est mis sous balayage d'argon avec un débit de 50 litres/heure, puis chauffé à une température de 1400°C. Cette température est ensuite maintenue pendant 5 heures. Après quoi, toujours sous balayage d'argon, le réacteur est refroidi jusqu'à la température ambiante.The carbon foam is then placed in a reactor on a bed consisting of an intimate mixture of silicon powder and silica. The reactor is placed under argon sweeping with a flow rate of 50 liters / hour, then heated to a temperature of 1400 ° C. This temperature is then maintained for 5 hours. After which, still under argon sweeping, the reactor is cooled to room temperature.
Le produit obtenu est une mousse de carbure de silicium qui se présente sous la forme d'une texture poreuse dont la macroporosité est constituée par les trous percés dans le précurseur, dont la microporosité a pratiquement disparu et dont la mésoporosité représente une surface spécifique de 35 m2/g. Les cristallites de carbure de silicium ont de faibles dimensions, comprises entre 40 et 400 angströms. Le produit ne contient que peu ou pas de métal résiduel, moins de 0,1 % en poids.The product obtained is a silicon carbide foam which is in the form of a porous texture whose macroporosity is formed by the holes drilled in the precursor, whose microporosity has practically disappeared and whose mesoporosity represents a specific surface of 35 m2 / g. The silicon carbide crystallites have small dimensions, between 40 and 400 angstroms. The product contains little or no residual metal, less than 0.1% by weight.
La perméabilité de ce carbure a été comparée à celle d'un support de catalyseur classique, en cordiérite, de même forme et de même dimension. Il s'agit, en effet, d'une caractéristique d'usage très importante pour les catalyseurs de pot d'échappement qui ne doivent pas provoquer de perte de charge trop importante dans l'écoulement à débit élevé des gaz d'échappement.
La perte de charge par unité de longueur P/l est donnée par la formule:
où
P est la perte de charge
l la longueur de l'échantillon
S la section de l'échantillon
µ la viscosité du fluide
m la masse volumique du fluide
d le débit de fluide
k₁ et k₂ deux coefficients caractéristiques de la perméabilité de l'échantillon.
Il faut noter que, toutes choses égales par ailleurs, la perte de charge P est d'autant plus faible, c'est-à-dire que la perméabilité est d'autant plus élevée que k₁ et k₂ sont plus grands.The permeability of this carbide has been compared with that of a conventional catalyst support, made of cordierite, of the same shape and the same size. This is, in fact, a very important feature of use for the exhaust catalysts which must not cause too great a pressure drop in the flow at high flow rate of the exhaust gases.
The pressure drop per unit length P / l is given by the formula:
or
P is the pressure drop
l the length of the sample
S section of the sample
µ the viscosity of the fluid
m the density of the fluid
d fluid flow
k₁ and k₂ two coefficients characteristic of the permeability of the sample.
It should be noted that, all other things being equal, the pressure drop P is all the lower, that is to say that the permeability is all the higher as k₁ and k₂ are greater.
Le tableau ci après donne les valeurs des coefficients k₁ et k₂ pour la mousse classique de cordiérite et pour la mousse en SiC.
Il ressort de ce tableau que le coefficient k₁ est 2,4 fois plus élevé et le coefficient k₂ 9,3 fois plus élevé pour le SiC que pour la cordiérite et que, par conséquent, le carbure de silicium est sensiblement plus perméable que la cordiérite.It appears from this table that the coefficient k₁ is 2.4 times higher and the coefficient k₂ 9.3 times higher for SiC than for cordierite and that, consequently, silicon carbide is appreciably more permeable than cordierite .
On a découpé dans un panneau de mousse de poluréthanne une pièce ayant approximativement la forme et les dimensions d'un catalyseur de pot d'échappement. Cette pièce a été lavée dans une solution aqueuse de soude à 4 % à 65°C pendant 8 minutes, puis rincée abondamment à l'eau courante, enfin séchée à l'étuve à 150°C pendant 30 minutes ou au four à micro-ondes pendant 15 minutes. La pièce sèche a été alors imprégnée avec une résine furfurylique additionnée de 2 % d'hexaméthylènetétramine et essorée de façon à ce qu'il reste 0,065 g de résine /cm³ de mousse. La mousse imprégnée a été ensuite pyrolysée jusque 1200°C dans les conditions de montée en température suivantes:
- a) 10°C/min jusque 250°C
- b) 1°C/min jusque 800°C
- c) 3°C/min jusque 1200°C
- d) palier de 2 heures à 1200°C.
- a) 10 ° C / min up to 250 ° C
- b) 1 ° C / min up to 800 ° C
- c) 3 ° C / min up to 1200 ° C
- d) 2 hour level at 1200 ° C.
La mousse de carbone ainsi obtenue possède une macroporosité suffisante pour l'accès des gaz, mais sa mésoporosité et sa microporosité sont insuffisantes. Il est donc nécessaire de procéder à son activation, dans les conditions de l'exemple 3 suivant avant de procéder à la carburation dans les conditions de l'exemple 1.The carbon foam thus obtained has a macroporosity sufficient for the access of the gases, but its mesoporosity and its microporosity are insufficient. It is therefore necessary to carry out its activation, under the conditions of example 3 below before proceeding to carburetion under the conditions of example 1.
On est parti d'une mousse de carbone du commerce de très faible masse volumique: 0,03 g/cm³ dont la surface BET est également très faible: moins de 1 m²/g.We started with a commercial carbon foam of very low density: 0.03 g / cm³ whose BET surface is also very small: less than 1 m² / g.
La mousse est placée dans un réacteur porté à une température de 900°C dans lequel on fait circuler du gaz carbonique débarrassé de traces d'oxygène, à raison de 200 litres / heure, mesurées dans les conditions normales de température et de pression. La réaction d'activation dure 2 heures, après quoi la mousse est refroidie jusqu'à l'ambiante sous circulation de gaz inerte. La mousse activée obtenue présente une surface spécifique BET considérablement augmentée, de 680 m²/g.The foam is placed in a reactor brought to a temperature of 900 ° C. in which carbon dioxide gas free of traces of oxygen is circulated, at the rate of 200 liters / hour, measured under normal conditions of temperature and pressure. The activation reaction lasts 2 hours, after which the foam is cooled to room temperature under circulation of inert gas. The activated foam obtained has a considerably increased BET specific surface area of 680 m² / g.
Un échantillon de la mousse activée obtenue selon les conditions de l'exemple 3 est placé dans un réacteur sur un lit constitué d'un mélange intime de poudre de silicium et de silice. Le réacteur est mis sous balayage d'argon avec un débit de 50 litres/heure, puis chauffé à une température de 1400°C. Cette température est ensuite maintenue pendant 5 heures. Après quoi, toujours sous balayage d'argon, le réacteur est refroidi jusqu'à la température ambiante.A sample of the activated foam obtained according to the conditions of Example 3 is placed in a reactor on a bed consisting of an intimate mixture of silicon powder and silica. The reactor is placed under argon sweeping with a flow rate of 50 liters / hour, then heated to a temperature of 1400 ° C. This temperature is then maintained for 5 hours. After which, still under argon sweeping, the reactor is cooled to room temperature.
La réaction est pilotée par la pression partielle de CO dans le gaz de balayage à la sortie du réacteur: quand cette pression partielle dépasse 2 hPa, on augmente le débit d'argon; quand cette pression descend en-dessous de 0,05 hPa, ce débit est ramené à sa valeur initiale.The reaction is controlled by the partial pressure of CO in the purging gas at the outlet of the reactor: when this partial pressure exceeds 2 hPa, the flow of argon is increased; when this pressure drops below 0.05 hPa, this flow rate is reduced to its initial value.
La mousse de carbure de silicium est ensuite traitée par de l'air à une température comprise entre 600 et 800°C pour éliminer le reste de la mousse activée qui n'aurait pas réagi.The silicon carbide foam is then treated with air at a temperature between 600 and 800 ° C to remove the rest of the activated foam which has not reacted.
On obtient une mousse de carbure de silicium ayant les caractéristiques suivantes:
- composition de la mousse: 100 % de SiC beta; 0 % de carbone résiduel; 0 % de silicium.
- diamètre des cristallites: 52 angströms.
- surface BET:
avant traitement d'oxydation: 19 m²/g
après traitement d'oxydation: 22 m²/g
- foam composition: 100% SiC beta; 0% residual carbon; 0% silicon.
- diameter of the crystallites: 52 angstroms.
- BET surface:
before oxidation treatment: 19 m² / g
after oxidation treatment: 22 m² / g
Un échantillon de la mousse obtenue selon les conditions de l'exemple 1 est placé dans un réacteur sur un lit constitué d'oxyde de molybdène MoO₃. Le réacteur est mis sous balayage d'argon avec un débit de 50 litres/heure, puis chauffé à une température de 1300°C. Cette température est ensuite maintenue pendant 5 heures. Après quoi, toujours sous balayage d'argon, le réacteur est refroidi jusqu'à la température ambiante.A sample of the foam obtained according to the conditions of Example 1 is placed in a reactor on a bed consisting of molybdenum oxide MoO₃. The reactor is placed under an argon sweep with a flow rate of 50 liters / hour, then heated to a temperature of 1300 ° C. This temperature is then maintained for 5 hours. After which, still under argon sweeping, the reactor is cooled to room temperature.
On obtient une mousse de carbure de molybdène Mo₂C ayant les caractéristiques suivantes:
- composition de la mousse: 83 % de Mo₂C ; 17 % de carbone résiduel; 0 % de molybdène métal.
- diamètre des cristallites: 270 angströms.
- surface BET: 150 m²/g
- foam composition: 83% Mo₂C; 17% residual carbon; 0% molybdenum metal.
- diameter of the crystallites: 270 angstroms.
- BET surface: 150 m² / g
La mousse de carbure de silicium obtenue selon les conditions de l'exemple 4 a été comparée avec des granulés de SiC de dimensions comprises entre 1,25 et 2,5 mm préparés à partir de charbon actif d'une part selon les conditions de la demande française 2 621 904, c'est-à-dire sous un vide de 10⁻² mm de mercure (1,333 Pa), d'autre part selon des conditions voisines dans lesquelles le vide a été remplacé par un balayage d'argon.The silicon carbide foam obtained according to the conditions of Example 4 was compared with SiC granules of dimensions between 1.25 and 2.5 mm prepared from activated carbon on the one hand according to the conditions of the French application 2,621,904, that is to say under a vacuum of 10⁻² mm of mercury (1.333 Pa), on the other hand according to similar conditions in which the vacuum has been replaced by an argon sweep.
Les conditions de synthèse et les caractéristiques obtenues figurent dans le tableau ci-après:
Dans ce tableau, les tailles des cristallites (6ème colonne) sont exprimées en angström = 10⁻¹⁰ m; les 7ème et 8ème colonnes donnent la surface BET, exprimée en m²/g, respectivement avant et après le traitement d'oxydation destiné à éliminer le carbone résiduel. La composition des phases (4ème colonne) est donnée évidemment avant ce traitement.In this table, the sizes of the crystallites (6th column) are expressed in angström = 10⁻¹⁰ m; the 7th and 8th columns give the BET surface, expressed in m² / g, respectively before and after the oxidation treatment intended to remove the residual carbon. The composition of the phases (4th column) is obviously given before this treatment.
Les conclusions que l'on tire de l'examen de ce tableau sont:
- les surfaces BET qui sont une caractéristique importante pour l'utilisation de ces produits comme catalyseurs ou supports de catalyseurs sont du même ordre pour les trois produits.
- l'utilisation de mousse de carbone permet d'obtenir une taille de cristallites nettement plus fine que les procédés à partir de charbon actif, qu'ils soient sous vide ou sous gaz inerte.
- la substitution d'un balayage d'argon au vide permet de réduire de façon notable les durées de traitement: de 8 à 5 heures.
- the BET surfaces which are an important characteristic for the use of these products as catalysts or catalyst supports are of the same order for the three products.
- the use of carbon foam makes it possible to obtain a much finer crystallite size than the processes using activated carbon, whether they are under vacuum or under inert gas.
- the substitution of an argon sweep for the vacuum makes it possible to significantly reduce the treatment times: from 8 to 5 hours.
Claims (18)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR919114607A FR2684092B1 (en) | 1991-11-21 | 1991-11-21 | PROCESS FOR THE PREPARATION OF LARGE SPECIFIC METAL CARBIDES FROM ACTIVATED CARBON FOAMS. |
FR9114607 | 1991-11-21 |
Publications (2)
Publication Number | Publication Date |
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EP0543752A1 true EP0543752A1 (en) | 1993-05-26 |
EP0543752B1 EP0543752B1 (en) | 1996-02-14 |
Family
ID=9419366
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Application Number | Title | Priority Date | Filing Date |
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EP92420429A Expired - Lifetime EP0543752B1 (en) | 1991-11-21 | 1992-11-19 | Process for preparing metal carbides of high specific surface from activated carbon foams |
Country Status (13)
Country | Link |
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US (1) | US6217841B1 (en) |
EP (1) | EP0543752B1 (en) |
JP (1) | JP2564234B2 (en) |
KR (1) | KR960014906B1 (en) |
AU (1) | AU655086B2 (en) |
BR (1) | BR9204503A (en) |
DE (1) | DE69208329T2 (en) |
DK (1) | DK0543752T3 (en) |
ES (1) | ES2083716T3 (en) |
FI (1) | FI925292A (en) |
FR (1) | FR2684092B1 (en) |
NO (1) | NO924432L (en) |
ZA (1) | ZA928947B (en) |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4481179A (en) * | 1983-10-12 | 1984-11-06 | The United States Of America As Represented By The United States Department Of Energy | Method for forming fibrous silicon carbide insulating material |
US4536358A (en) * | 1982-06-17 | 1985-08-20 | Uop Inc. | Process for the production of high surface area catalyst supports |
FR2621904A1 (en) * | 1987-10-19 | 1989-04-21 | Pechiney Electrometallurgie | Process for the production of silicon carbide, having a high specific surface, for catalyst substrate |
EP0315453A2 (en) * | 1987-11-03 | 1989-05-10 | Alcan International Limited | Porous membranes of sinterable refractory metal oxides or silica |
FR2645143A1 (en) * | 1989-03-28 | 1990-10-05 | Pechiney Electrometallurgie | Production of heavy metal carbides of high specific surface |
EP0440569A2 (en) * | 1990-01-29 | 1991-08-07 | PECHINEY RECHERCHE (Groupement d'Intérêt Economique régi par l'Ordonnance du 23 Septembre 1967) | Process for obtaining refractory carbide based porous solid bodies, using organic compounds and a metal or metalloid |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3345440A (en) * | 1965-06-29 | 1967-10-03 | John M Googin | Method for manufacturing foam carbon products |
US3859421A (en) * | 1969-12-05 | 1975-01-07 | Edward E Hucke | Methods of producing carbonaceous bodies and the products thereof |
JPS50148292A (en) * | 1974-05-22 | 1975-11-27 | ||
JPS54122312A (en) * | 1978-03-15 | 1979-09-21 | Hiroshige Suzuki | Silicon carbide powder for sintering use and preparation thereof |
DE2852410C2 (en) * | 1978-12-04 | 1981-12-03 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Process and device for the production of silicon carbide molded bodies |
DE3008590A1 (en) * | 1980-03-06 | 1981-09-17 | Bayer Ag, 5090 Leverkusen | SOLUTIONS OF POLYURETHANES IN POLYOLS AND THE USE THEREOF IN A METHOD FOR PRODUCING POLYURETHANE PLASTICS |
EP0050627A1 (en) * | 1980-04-28 | 1982-05-05 | Johnson Matthey Public Limited Company | Porous carbons |
JPS5833167A (en) * | 1981-08-21 | 1983-02-26 | Hioki Denki Kk | Current measurement |
JPS59156905A (en) * | 1983-02-25 | 1984-09-06 | Tsuchiya Mfg Co Ltd | Porous structure made of activated carbon and its manufacture |
JPS60191013A (en) * | 1984-03-09 | 1985-09-28 | Taiheiyo Randamu Kk | Manufacture of spherical silicon carbide powder |
JPS60195069A (en) * | 1984-03-16 | 1985-10-03 | 株式会社トクヤマ | Porous ceramic and manufacture |
CA1291110C (en) * | 1985-11-18 | 1991-10-22 | Christopher John Carruthers Edwards | Porous carbon structures and methods for their preparation |
US4915924A (en) * | 1987-08-12 | 1990-04-10 | Alcan International Limited | Method of preparing whiskers of silicon carbide and other materials |
US4914070A (en) | 1987-10-19 | 1990-04-03 | Pechiney Electrometallurgie | Process for the production of silicon carbide with a large specific surface area and use for high-temperature catalytic reactions |
DE3832876A1 (en) * | 1988-09-28 | 1990-04-05 | Hoechst Ceram Tec Ag | COMPONENTS MADE OF SILICON-INFILTRATED SILICON CARBIDE WITH POROESE SURFACE AND METHOD FOR THEIR PRODUCTION |
ATE124666T1 (en) * | 1989-03-28 | 1995-07-15 | Pechiney Recherche | PRODUCTION OF HEAVY METAL CARBIDES WITH INCREASED SPECIFIC SURFACE AREA. |
-
1991
- 1991-11-21 FR FR919114607A patent/FR2684092B1/en not_active Expired - Fee Related
-
1992
- 1992-11-17 NO NO92924432A patent/NO924432L/en unknown
- 1992-11-19 ZA ZA928947A patent/ZA928947B/en unknown
- 1992-11-19 EP EP92420429A patent/EP0543752B1/en not_active Expired - Lifetime
- 1992-11-19 DK DK92420429.0T patent/DK0543752T3/en active
- 1992-11-19 DE DE69208329T patent/DE69208329T2/en not_active Expired - Fee Related
- 1992-11-19 ES ES92420429T patent/ES2083716T3/en not_active Expired - Lifetime
- 1992-11-20 JP JP4312176A patent/JP2564234B2/en not_active Expired - Fee Related
- 1992-11-20 FI FI925292A patent/FI925292A/en not_active Application Discontinuation
- 1992-11-20 BR BR9204503A patent/BR9204503A/en not_active IP Right Cessation
- 1992-11-20 AU AU28531/92A patent/AU655086B2/en not_active Ceased
- 1992-11-21 KR KR1019920022009A patent/KR960014906B1/en not_active IP Right Cessation
-
1994
- 1994-07-20 US US08/278,107 patent/US6217841B1/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4536358A (en) * | 1982-06-17 | 1985-08-20 | Uop Inc. | Process for the production of high surface area catalyst supports |
US4481179A (en) * | 1983-10-12 | 1984-11-06 | The United States Of America As Represented By The United States Department Of Energy | Method for forming fibrous silicon carbide insulating material |
FR2621904A1 (en) * | 1987-10-19 | 1989-04-21 | Pechiney Electrometallurgie | Process for the production of silicon carbide, having a high specific surface, for catalyst substrate |
EP0315453A2 (en) * | 1987-11-03 | 1989-05-10 | Alcan International Limited | Porous membranes of sinterable refractory metal oxides or silica |
FR2645143A1 (en) * | 1989-03-28 | 1990-10-05 | Pechiney Electrometallurgie | Production of heavy metal carbides of high specific surface |
EP0440569A2 (en) * | 1990-01-29 | 1991-08-07 | PECHINEY RECHERCHE (Groupement d'Intérêt Economique régi par l'Ordonnance du 23 Septembre 1967) | Process for obtaining refractory carbide based porous solid bodies, using organic compounds and a metal or metalloid |
Non-Patent Citations (1)
Title |
---|
WORLD PATENTS INDEX LATEST, semaine 8546, accession no. 85-286190, Derwent Publications Ltd, Londres, GB; & JP-A-60 195 069 (TOKUYAMA SODA K.K.) 03-10-1985 * |
Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997019019A1 (en) * | 1994-11-17 | 1997-05-29 | Elf Aquitaine Production | Method and catalyst for catalytically oxidising a low concentration of h2s in a gas to give sulphur |
FR2727101A1 (en) * | 1994-11-17 | 1996-05-24 | Elf Aquitaine | Direct oxidn. of hydrogen sulphide to sulphur |
US6083471A (en) * | 1994-11-17 | 2000-07-04 | Elf Exploration Production | Method and catalyst for catalytically oxidizing a low concentration of H2 S in a gas to give sulphur |
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FR2732336A1 (en) * | 1995-03-29 | 1996-10-04 | Aerospatiale | METHOD FOR PRODUCING A SELF-REPLACING SIC STRUCTURE OF THE SANDWICH TYPE WITH A HONEYCOMB SAME AND STRUCTURE THUS OBTAINED |
US6187123B1 (en) | 1995-03-29 | 2001-02-13 | Aerospatiale Societe Nationale Industrielle | Method for producing a lightened SiC sandwich type structure with a honeycomb-shaped core and structure obtained by said method |
US5888610A (en) * | 1995-06-08 | 1999-03-30 | Aerospatiale Societe Nationale Industrielle | Method for producing a panel or the like with structural and acoustic properties and panel obtained by said method |
US6267838B1 (en) | 1995-06-09 | 2001-07-31 | Aerospatiale Societe Nationale Industrielle | Sandwich panel made of a composite material and production method |
CN1072605C (en) * | 1995-11-20 | 2001-10-10 | 埃勒夫勘探产品公司 | Method and catalyst for catalytically oxidising a low concentration of H2S in a gas to give sulphur |
WO1997026988A1 (en) * | 1996-01-26 | 1997-07-31 | Pechiney Recherche | METAL OXIDE-COATED SiC FOAM CARRIERS FOR CATALYSTS, AND CATALYTIC SYSTEMS THEREFOR |
FR2744038A1 (en) * | 1996-01-26 | 1997-08-01 | Pechiney Recherche | CERINE COATED SIC FOAM CATALYST BRACKETS AND CORRESPONDING CATALYTIC SYSTEMS |
US5958831A (en) * | 1996-10-21 | 1999-09-28 | Pechiney Recherche | SiC foam catalyst carrier with a reinforced skin and corresponding catalytic systems |
FR2754741A1 (en) * | 1996-10-21 | 1998-04-24 | Pechiney Recherche | SIC FOAM CATALYST SUPPORT WITH REINFORCED SKIN AND CORRESPONDING CATALYST SYSTEMS |
EP0836882A1 (en) * | 1996-10-21 | 1998-04-22 | PECHINEY RECHERCHE (Groupement d'Intérêt Economique géré par l'ordonnance du 23 Septembre 1967) | Catalyst support made of SiC foam with a reinforced skin and catalytic systems accordingly |
FR2758279A1 (en) * | 1997-01-13 | 1998-07-17 | Pechiney Recherche | SILICON CARBIDE CATALYST SUPPORT WITH HIGH SPECIFIC SURFACE IN PELLET FORM HAVING IMPROVED MECHANICAL CHARACTERISTICS |
WO1998030328A1 (en) * | 1997-01-13 | 1998-07-16 | Pechiney Recherche | Catalyst support with base of silicon carbide with high specific surface area in granulated form having improved mechanical characteristics |
US6184178B1 (en) * | 1997-01-13 | 2001-02-06 | Pechiney Recherche | Catalyst support with base of silicon carbide with high specific surface area in granulated form having improved mechanical characteristics |
FR2766389A1 (en) * | 1997-07-25 | 1999-01-29 | Pechiney Recherche | SILICON CARBIDE FOAM WITH A HIGH SPECIFIC SURFACE AND IMPROVED MECHANICAL CHARACTERISTICS |
WO1999004900A1 (en) * | 1997-07-25 | 1999-02-04 | Pechiney Recherche | Silicon carbide foam with high specific surface area and improved mechanical properties |
US6372193B1 (en) | 1998-09-24 | 2002-04-16 | Elf Exploration Production | Process for oxidizing the H2S contained at low concentration in a gas directly to sulphur by catalytic means and in the vapour pause |
WO2001010771A1 (en) * | 1999-08-09 | 2001-02-15 | New Zealand Pump Company Limited | Fluid coupling and container |
EP1342703A2 (en) | 2002-03-04 | 2003-09-10 | Schunk Kohlenstofftechnik GmbH | Process for making a shaped carbonaceous body |
EA011114B1 (en) * | 2003-07-31 | 2008-12-30 | Синвеншн Аг | Method for the production of porous carbon-based molded bodies and use thereof |
WO2005021462A1 (en) * | 2003-07-31 | 2005-03-10 | Blue Membranes Gmbh | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
SG154326A1 (en) * | 2003-07-31 | 2009-08-28 | Cinv Ag | Method for the production of porous carbon-based moulded bodies, and use thereof as cell culture carrier systems and culture systems |
EP2025657A2 (en) | 2003-07-31 | 2009-02-18 | Cinvention Ag | Method for manufacturing carbon based shapes and their use as cell culture bearing and cultivation systems |
EP1658248A1 (en) * | 2003-07-31 | 2006-05-24 | Blue Membranes GmbH | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
WO2005038204A1 (en) * | 2003-10-16 | 2005-04-28 | Sicat | Catalytic filter made from silicon carbide ($g(b)-sic) for the combustion of soot from exhaust gases of an internal combustion engine |
US7479265B2 (en) | 2003-10-16 | 2009-01-20 | Sicat | Catalytic filter based on silicon carbide (β-SiC) for combustion of soot derived from exhaust gases from an internal combustion engine |
FR2860992A1 (en) * | 2003-10-16 | 2005-04-22 | Sicat | Production of beta silicon carbide foam filter material used for removing particulates from diesel engine exhaust gases comprises using polyurethane foam with at least two zones of different pore size distribution |
FR2860993A1 (en) * | 2003-10-16 | 2005-04-22 | Sicat | Silicon carbide-based catalytic sponge production for elimination of soot particles from exhaust gas of diesel engine |
US7393877B2 (en) | 2003-12-31 | 2008-07-01 | Total France | Process for the conversion of a synthesis gas to hydrocarbons in the presence of beta-SiC and effluent from this process |
WO2009098393A3 (en) * | 2007-11-30 | 2009-11-05 | Centre National De La Recherche Scientifique | Chemical reactor with nanometric superstructure |
WO2009098393A2 (en) * | 2007-11-30 | 2009-08-13 | Centre National De La Recherche Scientifique | Chemical reactor with nanometric superstructure |
US8574419B2 (en) | 2007-11-30 | 2013-11-05 | Centre National De La Recherche Scientifique | Chemical reactor with nanometric superstructure |
FR2925356A1 (en) * | 2007-12-21 | 2009-06-26 | Sicat Sarl | Oxidation of a gas containing hydrogen sulfide into sulfur, comprises contacting the gas with a catalyst comprising a support made of porous foam and an active phase containing a transition metal element |
WO2009103895A3 (en) * | 2007-12-21 | 2009-10-15 | Sicat | Method for oxidising h2s into sulphur using a catalyst carried by a porous sic foam |
WO2009103895A2 (en) * | 2007-12-21 | 2009-08-27 | Sicat | Method for oxidising h2s into sulphur using a catalyst carried by a porous sic foam |
EP2204236A1 (en) | 2008-12-19 | 2010-07-07 | Total Petrochemicals Research Feluy | Catalyst and process for hydrogenation of hydrocarbon feedstocks |
EP2204235A1 (en) | 2008-12-19 | 2010-07-07 | Total Petrochemicals Research Feluy | Catalyst and process for selective hydrogenation of alkynes and dienes |
WO2014207096A1 (en) * | 2013-06-27 | 2014-12-31 | Sicat | Method for manufacturing shaped beta-sic mesoporous products and products obtained by this method |
FR3007673A1 (en) * | 2013-06-27 | 2015-01-02 | Sicat | PROCESS FOR PRODUCING BETA-SIC MESOPOROUS FORMAL PRODUCTS AND PRODUCTS OBTAINED THEREBY |
Also Published As
Publication number | Publication date |
---|---|
BR9204503A (en) | 1994-02-22 |
US6217841B1 (en) | 2001-04-17 |
FI925292A (en) | 1993-05-22 |
DK0543752T3 (en) | 1996-03-11 |
JPH05254816A (en) | 1993-10-05 |
KR960014906B1 (en) | 1996-10-21 |
AU2853192A (en) | 1993-05-27 |
ES2083716T3 (en) | 1996-04-16 |
EP0543752B1 (en) | 1996-02-14 |
DE69208329T2 (en) | 1996-07-04 |
FI925292A0 (en) | 1992-11-20 |
FR2684092B1 (en) | 1994-03-04 |
JP2564234B2 (en) | 1996-12-18 |
NO924432L (en) | 1993-05-24 |
NO924432D0 (en) | 1992-11-17 |
KR930009919A (en) | 1993-06-21 |
AU655086B2 (en) | 1994-12-01 |
FR2684092A1 (en) | 1993-05-28 |
ZA928947B (en) | 1993-05-17 |
DE69208329D1 (en) | 1996-03-28 |
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